Cleaning agent composition comprising an alkylamide solvent and a fluorine-containing quaternary ammonium salt

ABSTRACT

A cleaning agent composition for use in removing an adhesive residue, characterized in that the composition contains a quaternary ammonium salt and a composition solvent including a first organic solvent and a second organic solvent; the first organic solvent is an amide derivative represented by formula (Z) (wherein R0 represents an ethyl group, a propyl group, or an isopropyl group; and each of RA and RB represents a C1 to C4 alkyl group); the second organic solvent is a non-amide organic solvent other than the amide derivative; and the composition has a water content less than 4.0 mass %.

TECHNICAL FIELD

The present invention relates to a cleaning agent composition and to acleaning method.

BACKGROUND ART

Conventionally, electronic elements and wires are 2-dimensionally(within a plane) integrated on a semiconductor wafer. In a trend towardfurther integration, demand has arisen for a semiconductor integrationtechnique which achieves 3-dimensional integration (i.e., stacking) inaddition to 2-dimensional integration. In the technique of 3-dimensionalintegration, a number of layers are stacked with wire connection by themediation of through silicon vias (TSVs). In integration of multiplelayers, each component wafer to be stacked is thinned by polishing(i.e., grinding) a surface opposite the circuit-furnished surface (i.e.,a back surface), and the thus-thinned semiconductor wafers are stacked.

Before thinning, the semiconductor wafer (may also be called simply“wafer”) is fixed to a support for facilitating polishing by means of apolishing machine (i.e., grinder). Since the fixation must be easilyremoved after polishing, the fixation is called temporary bonding.Temporary bonding must be easily removed from the support. When suchtemporary bonding is removed by excessive force, in some cases a thinnedsemiconductor wafer may be broken or deformed. In order to prevent sucha phenomenon, the temporarily bonded support is detached in a gentlemanner. However, from another aspect, it is not preferred that thetemporarily bonded support be removed or slid by a stress applied duringpolishing of the back surface of the semiconductor wafer. Therefore,temporary bonding must withstand the stress during polishing and must beeasily removed after polishing. For example, one required performanceincludes having high stress (i.e., strong adhesion) within the planeduring polishing and low stress (i.e., weak adhesion) toward thethickness direction during detaching. Furthermore, in processing steps,the temperature of a workpiece may exceed 150° C. in some cases. Thus,temporary bonding must be stable at such high temperatures.

Under such circumstances, polysiloxane adhesives meeting theaforementioned characteristic requirements are mainly used as temporaryadhesives in the semiconductor industry. In temporary bonding by use ofa polysiloxane adhesive, an adhesive residue often remains on asubstrate surface after removal of the thinned substrate. In order toavoid an undesired phenomenon in a subsequent step, there has beendeveloped a cleaning agent composition for removing such a residue andcleaning the surface of a semiconductor substrate (see, for example,Patent Documents 1 and 2). Currently, there is continuous demand for anew cleaning agent composition in the semiconductor field. PatentDocument 1 discloses a siloxane resin-remover containing a polar,aprotic solvent and a quaternary ammonium hydroxide, and Patent Document2 discloses a cured resin-remover containing an alkylammonium fluoride.However, development of a more effective cleaning agent composition isexpected.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: WO 2014/092022-   Patent Document 2: U.S. Pat. No. 6,818,608-   Patent Document 3: Korean Patent Application Laid-Open 2014-0064401-   Patent Document 4: Korean Patent Application Laid-Open 2014-0024625-   Patent Document 5: Korean Patent Application Laid-Open 2016-0017606

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

The present invention has been conceived in view of the foregoing. Thus,an object of the invention is to provide a cleaning agent compositionwhich exhibits excellent cleaning performance to an adhesive residueremaining after debonding a laminate that has been temporarily bonded bythe mediation of an adhesive layer formed from, for example, apolysiloxane adhesive. Another object is to provide a cleaning methodusing such a cleaning agent composition.

Means for Solving the Problems

The present inventors have conducted extensive studies to attain theaforementioned objects, and have found the following. In cleaning of asubstrate (e.g., a semiconductor substrate) on which an adhesive residueremains after debonding a laminate that has been temporarily bonded bythe mediation of an adhesive layer formed from a polysiloxane adhesive,when a cleaning agent composition containing a quaternary ammonium saltand a solvent is employed, a specific amide derivative and a non-amideorganic solvent other than the amide derivative are used in combinationas the solvent. Also, the water content of the cleaning agentcomposition is regulated to a level lower than a specific value. As aresult, a cleaning agent composition that has excellent cleaningperformance and that can shorten cleaning time can be provided. Thepresent invention has been accomplished on the basis of this finding.

Notably, Patent Documents 3 to 5 disclose a photoresist removercomposition and a cleaning agent composition each employingN,N-dimethylpropionamide. However, none of Patent Documents 3 to 5specifically discloses the technical feature and advantageous effects ofthe present invention.

Accordingly, the present invention provides the following.

1. A cleaning agent composition for use in removing an adhesive residue,characterized in that

the composition comprises a quaternary ammonium salt and a compositionsolvent including a first organic solvent and a second organic solvent;

the first organic solvent is an amide derivative represented by formula(Z):

(wherein R⁰ represents an ethyl group, a propyl group, or an isopropylgroup; and each of R^(A) and R^(B) represents a C1 to C4 alkyl group);

the second organic solvent is a non-amide organic solvent other than theamide derivative; and

the composition has a water content less than 4.0 mass %.

2. A cleaning agent composition according to 1 above, wherein the amidederivative includes at least one species selected from the groupconsisting of N,N-dimethylpropionamide, N,N-diethylpropionamide,N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide,N,N-diethylbutyramide, N-ethyl-N-methylbutyramide,N,N-dimethylisobutyramide, N,N-diethylisobutyramide, andN-ethyl-N-methylisobutyramide.

3. A cleaning agent composition according to 2 above, wherein the amidederivative includes at least one species selected from the groupconsisting of N,N-dimethylpropionamide, N,N-diethylpropionamide,N,N-dimethylbutyramide, N,N-diethylbutyramide,N,N-dimethylisobutyramide, and N,N-diethylisobutyramide.

4. A cleaning agent composition according to 3 above, wherein the amidederivative includes at least one species selected from the groupconsisting of N,N-dimethylpropionamide and N,N-dimethylisobutyramide.

5. A cleaning agent composition according to any of 1 to 4 above,wherein the quaternary ammonium salt includes a halogen-containingquaternary ammonium salt.

6. A cleaning agent composition according to 5 above, wherein thehalogen-containing quaternary ammonium salt include afluorine-containing quaternary ammonium salt.

7. A cleaning agent composition according to 6 above, wherein thefluorine-containing quaternary ammonium salt includes atetra(hydrocarbyl)ammonium fluoride.

8. A cleaning agent composition according to 7 above, wherein thetetra(hydrocarbyl)ammonium fluoride includes at least one speciesselected from the group consisting of tetramethylammonium fluoride,tetraethylammonium fluoride, tetrapropylammonium fluoride, andtetrabutylammonium fluoride.

9. A cleaning agent composition according to any of 1 to 8 above,wherein the second organic solvent includes at least one speciesselected from the group consisting of an alkylene glycol dialkyl ether,an aromatic hydrocarbon compound, and a ring-structure-having ethercompound.

10. A cleaning agent composition according to any of 1 to 9 above,wherein the composition solvent is formed only of an organic solvent.

11. A cleaning agent composition according to any of 1 to 10 above,wherein the composition solvent has an amide derivative content of 30 to90 mass %.

12. A cleaning agent composition according to any of 1 to 11 above,which has a water content less than 3.0 mass %.

13. A cleaning agent composition according to 12 above, which has awater content less than 2.0 mass %.

14. A cleaning agent composition according to 13 above, which has awater content less than 1.0 mass %.

15. A cleaning method, characterized by comprising removing an adhesiveresidue remaining on a substrate by use of a cleaning agent compositionas recited in any of 1 to 14 above.

16. A method for producing a processed semiconductor substrate, themethod comprising a first step of producing a laminate including asemiconductor substrate, a support substrate, and an adhesive layerformed from an adhesive composition; a second step of processing thesemiconductor substrate of the produced laminate; a third step ofseparating the semiconductor substrate after processing; and a fourthstep of removing an adhesive residue remaining on the separatedsubstrate with a cleaning agent composition, characterized in that acleaning agent composition as recited in any of 1 to 14 above is used asthe cleaning agent composition.

Effects of the Invention

According to the cleaning agent composition of the present invention, asubstrate (e.g., a semiconductor substrate) on which an adhesive residueremains after debonding a laminate which has been temporarily bonded bythe mediation of an adhesive layer formed from a material (e.g., apolysiloxane adhesive) can be cleaned in a short period of time in asimple manner. As a result, high-efficiency production of semiconductordevices is expacted.

MODES FOR CARRYING OUT THE INVENTION

The present invention will next be described in detail.

The cleaning agent composition of the present invention contains aquaternary ammonium salt.

A quaternary ammonium salt is formed of a quaternary ammonium cation andan anion. No particular limitation is imposed on the quaternary ammoniumsalt, so long as the salt is used for such a cleaning agent composition.

A typical example of such a quaternary ammonium cation is atetra(hydrocarbyl)ammonium cation. Examples of the counter anioninclude, but are not limited to, a hydroxide ion (OH⁻); a halide ionsuch as a fluoride ion (F⁻), a chloride ion (Cl⁻), a bromide ion (Br⁻),or an iodide ion (I⁻); a tetrafluoroborate ion (BF₄ ⁻); and ahexafluorophosphate ion (PF₆ ⁻).

In the present invention, the quaternary ammonium salt preferablyincludes a halogen-containing quaternary ammonium salt, more preferablya fluorine-containing quaternary ammonium salt.

In the quaternary ammonium salt, a halogen atom may be included in acation moiety or an anion moiety. Preferably, the halogen atom isincluded in an anion moiety.

In one preferred embodiment, the fluorine-containing quaternary ammoniumsalt includes a tetra(hydrocarbyl)ammonium fluoride.

Specific examples of the hydrocarbyl group of thetetra(hydrocarbyl)ammonium fluoride include a C1 to C20 alkyl group, aC2 to C20 alkenyl group, a C2 to C20 alkynyl group, and a C6 to C20 arylgroup.

In one preferred embodiment of the present invention, thetetra(hydrocarbyl)ammonium fluoride includes a tetraalkylammoniumfluoride.

Specific examples of the tetraalkylammonium fluoride include, but arenot limited to, tetramethylammonium fluoride, tetraethylammoniumfluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.Among them, tetrabutylammonium fluoride (i.e., TBAF) is preferred.

The quaternary ammonium salt such as tetra(hydrocarbyl)ammonium fluoridemay be used in the form of a hydrate. Also, the quaternary ammonium saltsuch as tetra(hydrocarbyl)ammonium fluoride and a hydrate thereof may beused singly or in combination of two or more species.

So long as the quaternary ammonium salt can be dissolved in the solventcontained in the cleaning agent composition, no particular limitation isimposed on the amount of the salt, and the amount is generally 0.1 to 30mass % with respect to the cleaning agent composition.

The cleaning agent composition of the present invention contains acomposition solvent including a first organic solvent and a secondorganic solvent, wherein the first organic solvent is an amidederivative represented by formula (Z):

and the second organic solvent is a non-amide organic solvent other thanthe amide derivative.

In formula (Z), R⁰ represents an ethyl group, a propyl group, or anisopropyl group, with ethyl and isopropyl being preferred, and ethylbeing more preferred. Each of R^(A) and R^(B) represents a C1 to C4alkyl group. The C1 to C4 alkyl group may be linear-chain, branched, orcyclic. Specific examples include methyl, ethyl, propyl, isopropyl,cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and cyclobutyl. Amongthem, both R^(A) and R^(B) are preferably methyl or ethyl, and, morepreferably, each of R^(A) and R^(B) is methyl.

Examples of the amide derivative represented by formula (Z) include, butare not limited to, N,N-dimethylpropionamide, N,N-diethylpropionamide,N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide,N,N-diethylbutyramide, N-ethyl-N-methylbutyramide,N,N-dimethylisobutyramide, N,N-diethylisobutyramide, andN-ethyl-N-methylisobutyramide. These amide derivatives represented byformula (Z) may be used singly or in combination of two or more species.

Of these, N,N-dimethylpropionamide and N,N-dimethylisobutylamide areparticularly preferred, with N,N-dimethylpropionamide being morepreferred.

The amide derivative represented by formula (Z) may be synthesizedthrough substitution of a corresponding carboxylate ester with acorresponding amine. Alternatively, a commercial product of the amidederivative may also be used.

The cleaning agent composition of the present invention contains one ormore organic solvents other than the aforementioned amide derivative.

No particular limitation is imposed on the organic solvent other thanthe amide derivative, so long as the organic solvent is used in thetechnical field, can dissolve the quaternary ammonium salt, and iscompatible with the aforementioned amide derivative.

Examples of preferred such organic solvents include an alkylene glycoldialkyl ether.

Specific examples of the alkylene glycol dialkyl ether include, but arenot limited to, ethylene glycol, dimethyl ether (1,2-dimethoxyethane),ethylene glycol, diethyl ether (1,2-diethoxyethane), ethylene glycoldipropyl ethane, ethylene glycol dibutyl ether, propylene glycoldimethyl ether, propylene glycol diethyl ether, and propylene glycoldipropyl ether.

These alkylene glycol dialkyl ethers may be used singly or incombination of two or more species.

Examples of preferred such organic solvents include an aromatichydrocarbon compound, and specific examples thereof include aromatichydrocarbon compounds represented by formula (1).

In the above formula (1), specific examples of the C1 to C6 alkyl groupinclude methyl, ethyl, n-propyl, n-butyl, isobutyl, s-butyl, andt-butyl.

The “s” represents the number of the substituents R¹⁰⁰s bound to thebenzene ring and is 2 or 3.

In one preferred embodiment of the present invention, the aromatichydrocarbon compound represented by formula (1) is an aromatichydrocarbon compound represented by formula (1-1) or (1-2):

(wherein R¹⁰⁰s each represent a C1 to C6 alkyl group; the total numberof carbon atoms in three C1 to C6 alkyl groups of R¹⁰⁰ in formula (1-1)is 3 or greater; and the total number of carbon atoms in two C1 to C6alkyl groups of R¹⁰⁰ in formula (1-2) is 3 or greater).

Specific examples of the aromatic hydrocarbon compound represented byformula (1) include, but are not limited to, 1,2,3-trimethylbenzene,1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene(mesitylene), 4-ethyltoluene, 4-n-propyltoluene, 4-isopropyltoluene,4-n-butyltoluene, 4-s-butyltoluene, 4-isobutyltoluene, and4-t-butyltoluene. These aromatic hydrocarbon compounds may be usedsingly or in combination of two or more species.

Of these, mesitylene and 4-t-butyltoluene are preferred.

Examples of preferred such organic solvents include aring-structure-having ether compound. Examples of thering-structure-having ether compound include a cyclic ether compound, acyclic alkyl-chain alkyl ether compound, a cyclic alkyl-branch ethercompound, and a di(cyclic alkyl) ether compound. Thesering-structure-having ether compounds may be used singly or incombination or two or more species.

The ring-structure-having ether compound is produced by substituting atleast one ring-forming carbon atom of the cyclic hydrocarbon compound byan oxygen atom.

Typical examples of the ring-structure-having ether compound includeepoxy compounds formed through epoxidation of a chain, branched, orcyclic saturated hydrocarbon compound (i.e., the case in which the twoadjacent carbon atoms and the oxygen atom form a 3-membered ring) andcyclic ether compounds (excepting an epoxy compound, and the definitionwill apply hereinbelow) in which a carbon atom forming the ring of thecyclic hydrocarbon compound having carbon 4 atoms (excepting an aromatichydrocarbon compound) is substituted by an oxygen atom. Among them, thecyclic hydrocarbon compound having carbon 4 atoms is preferably a cyclicsaturated hydrocarbon compound having carbon 4 atoms.

No particular limitation is imposed on the number of the carbon atomspresent in the epoxy compound. The carbon number is generally 4 to 40,preferably 6 to 12.

No particular limitation is imposed on the number of epoxy groups, andthe number is generally 1 to 4, preferably 1 or 2.

Specific examples of the epoxy compound include, but are not limited to,epoxy chain or branched saturated hydrocarbon compounds such as1,2-epoxy-n-butane, 1,2-epoxy-n-pentane, 1,2-epoxy-n-hexane,1,2-epoxy-n-heptane, 1,2-epoxy-n-octane, 1,2-epoxy-n-nonane,1,2-epoxy-n-decane, and 1,2-epoxy-n-eicosane; and epoxy cyclic saturatedhydrocarbon compounds such as 1,2-epoxy-cyclopentane,1,2-epoxy-cyclohexane, 1,2-epoxy-cycloheptane, 1,2-epoxy-cyclooctane,1,2-epoxy-cyclononane, 1,2-epoxy-cyclodecane, and1,2-epoxy-cycloeicosane.

No particular limitation is imposed on the number of carbon atoms of thecyclic ether compound other than the aforementioned epoxy compounds isgenerally 3 to 40, preferably 4 to 8.

No particular limitation is imposed on the number of oxygen atoms (ethergroups), and the number is generally 1 to 3, preferably 1 or 2.

Specific examples of the cyclic ether compound other than theaforementioned epoxy compounds include, but are not limited to,oxacyclic saturated hydrocarbon compounds such as oxacyclobutane(oxetane), oxacyclopentane (tetrahydrofuran), and oxacyclohexane; anddioxacyclic saturated hydrocarbon compounds such as1,3-dioxacyclopentane, 1,3-dioxacyclohexane (1,3-dioxane), and1,4-dioxacyclohexane (1,4-dioxane).

The cycloalkyl (chain alkyl) ether compound is formed of a cycloalkylgroup and a chain alkyl group which are bound via an ether group. Noparticular limitation is imposed on the number of the carbon atomsforming the compound, and the carbon number is generally 4 to 40,preferably 5 to 20.

The cycloalkyl (branched alkyl) ether compound is formed of a cycloalkylgroup and a branched alkyl group which are bound via an ether group. Noparticular limitation is imposed on the number of the carbon atomsforming the compound, and the carbon number is generally 6 to 40,preferably 5 to 20.

The di(cycloalkyl) ether compound is formed of two cycloalkyl groupswhich are bound via an ether group. No particular limitation is imposedon the number of the carbon atoms forming the compound, and the carbonnumber is generally 6 to 40, preferably 10 to 20.

Of these, the cyclic ether compound other than the aforementioned epoxycompounds is preferably a cycloalkyl (chain alkyl) ether compound and acycloalkyl (branched alkyl) ether compound, with a cycloalkyl (chainalkyl) ether compound being more preferred.

The chain alkyl group is a group which is derived by deleting an endhydrogen atom of a corresponding linear-chain aliphatic hydrocarbon. Noparticular limitation is imposed on the chain alkyl group, and thecarbon number is generally 1 to 40, preferably 1 to 20.

Specific examples include, which are not limited to, methyl, ethyl,1-n-propyl, 1-n-butyl, 1-n-pentyl, 1-n-hexyl, 1-n-heptyl, 1-n-octyl,1-n-nonyl, and 1-n-decyl.

The branched alkyl group is a group which is derived by deleting ahydrogen atom of a corresponding linear-chain or branched aliphatichydrocarbon and which is a group other than chain alkyl groups. Noparticular limitation is imposed on the number of carbon atoms of thechain alky group, and the carbon number is generally 3 to 40, preferably3 to 20.

Specific examples include, which are not limited to, isopropyl,isobutyl, s-butyl, and t-butyl.

The cycloalkyl group a group which is derived by deleting a hydrogenatom bound to a ring-forming carbon atom of the corresponding cyclicaliphatic hydrocarbon. No particular limitation is imposed on the numberof carbon atoms, and the carbon number is generally 3 to 40, preferably5 to 20.

Specific examples include, which are not limited to, monocycloalkylgroups such as cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, andcyclohexyl; and bicycloalkyl groups such as bicyclo[2.2.1]heptan-1-yl,bicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.1]heptan-7-yl,bicyclo[2.2.2]octan-1-yl, bicyclo[2.2.2]octan-2-yl, andbicyclo[2.2.2]octan-7-yl.

Specific examples of the cycloalkyl (chain alkyl) ether compoundinclude, but are not limited to, cyclopentyl methyl ether (CPME),cyclopentyl ethyl ether, cyclopentyl propyl ether, cyclopentyl butylether, cyclohexyl methyl ether, cyclohexyl ethyl ether, cyclohexylpropyl ether, and cyclohexyl butyl ether.

Specific examples of the cycloalkyl (branched alkyl) ether compoundinclude, but are not limited to, cyclopentyl isopropyl ether andcyclopentyl t-butyl ether.

Specific examples of the di(cycloalkyl)ether compound include, but arenot limited to, dicyclopentyl ether, dicyclohexyl ether, and cyclopentylcyclohexyl ether.

In the solvent of the cleaning agent composition of the presentinvention, generally, the amide derivative is present in an amount of 30to 90 mass %, and the balance is the aforementioned non-amide organicsolvent(s).

The cleaning agent composition of the present invention has a watercontent less than 4.0 mass %. When the water content is 4 mass % ormore, the cleaning performance of the composition considerablydecreases. Although no precise reason therefor has been elucidated,conceivably, the quaternary ammonium salt present in the cleaning agentcomposition is adversely affected, to thereby impair the function of thecleaning agent composition. Notably, in the present invention, watercontent can be determined by means of, for example, a Karl Fischermoisture meter CA-200 (product of Mitsubishi Chemical Analytech).

From the viewpoint of providing a cleaning agent composition havingexcellent cleaning performance at high reproducibility, the watercontent of the cleaning agent composition of the present invention ispreferably less than 3.0 mass %, more preferably less than 2.0 mass %,still more preferably less than 1.5 mass %, further preferably less than1.0 mass %, yet more preferably less than 0.8 mass %.

Further, in a preferred embodiment of the present invention, the solventof the cleaning agent composition is formed only of organic solvents. Byuse of a totally organic solvent, a cleaning agent composition havingexcellent cleaning performance can be provided at high reproducibility.

Thus, the cleaning agent composition of the present invention generallycontains only organic solvents as the solvent components. Notably, theexpression “only organic solvent(s)” refers to the intended component ofthe solvent being formed of only an organic solvent, and does notexclude the presence of water unavoidably contained in the organicsolvent and in other components (e.g., a hydrate).

In other words, a technical feature of the cleaning agent composition ofthe present invention resides in that the composition containssubstantially no water. As described above, the concept “containingsubstantially no water” refers to “containing no intentionally addedwater” and does not exclude the presence of water attributable to ahydrate (other components) or the presence of a microamount of waterunavoidably incorporated into the composition with other components.

However, when the cleaning agent composition of the present inventionemploys only organic solvents as solvent components, the aforementionedwater content of the cleaning agent composition of the invention mustfall within the above-specified ranges.

The cleaning agent composition of the present invention may be preparedby mixing the aforementioned quaternary ammonium salt or a hydratethereof, the aforementioned first and second organic solvents, and otheroptional components. No particular limitation is imposed on the hydrate,and examples thereof include tetrabutylammonium fluoride trihydrate.

These ingredients may be mixed in any chronological order, so long asproblematic phenomena (e.g., precipitation of solid contents andseparation of the composition) do not eventually occur.

That is, a part of the ingredients of the cleaning agent composition maybe mixed in advance, followed by mixing of the other ingredients.Alternatively, all the ingredients may be mixed through a single mixingoperation. If required, the cleaning agent composition may be filtered.Alternatively, the supernatant of the mixed product is separated frominsoluble components and may be employed as the cleaning agentcomposition. Further, in the case where a certain ingredient employedhas hygroscopicity, deliquescency, or the like, the entire or a part ofthe steps of preparing the cleaning agent composition may be conductedunder inert gas.

The above-described cleaning agent composition of the present inventionexerts excellent cleansability to a polysiloxane adhesive and attains ahigh cleaning speed and an excellent cleaning persistency.

Specifically, the cleaning speed is determined as an etching rate[μm/min], which is determined by measuring a decrease in the layer(film) thickness of an adhesive layer obtained from an adhesivecomposition of interest after contact with the cleaning agentcomposition for 5 minutes at room temperature (23° C.) and dividing thevalue of decrease in the layer thickness by the time required forcleaning. The etching rate is generally 8.0 [μm/min] or greater, 9.0[μm/min] or greater in a preferred embodiment, 9.5 [μm/min] or greaterin a more preferred embodiment, 10.0 [μm/min] or greater in a still morepreferred embodiment, 10.5 [μm/min] or greater in a yet more preferredembodiment, and 11.0 [μm/min] or greater in a further more preferredembodiment

The cleaning persistency of the cleaning agent composition of thepresent invention is assessed by the time for dissolving 1 g of anadhesive solid obtained from an adhesive composition through contactwith the cleaning agent composition (2 g) at room temperature (23° C.).The cleaning persistency is generally 12 to 24 hours for substantialdissolution of the adhesive solid, 2 to 12 hours for completedissolution of the adhesive solid in a preferred embodiment, and 1 to 2hours for complete dissolution of the adhesive solid in a more preferredembodiment.

According to the present invention, a polysiloxane adhesive remaining ona substrate (e.g., a semiconductor substrate) is removed by use of theabove-described cleaning agent composition, whereby the substrate can becleaned within a short period of time. Thus, high-efficiency (favorable)cleaning of a substrate (e.g., a semiconductor substrate) can beachieved.

The cleaning agent composition of the present invention is used forsurface-cleaning of various substrates including semiconductorsubstrates. The cleaning target is not limited to a siliconsemiconductor substrate, and various substrates may be cleaned. Examplesof such substrates (cleaning targets) include a germanium substrate, agallium arsenide substrate, a gallium phosphide substrate, a galliumaluminum arsenide substrate, an aluminum-plated silicon substrate, acopper-plated silicon substrate, a silver-plated silicon substrate, agold-plated silicon substrate, a titanium-plated silicon substrate, asilicon nitride film-coated silicon substrate, a silicon oxidefilm-coated silicon substrate, a polyimide film-coated siliconsubstrate, a glass substrate, a quartz substrate, a liquid crystalsubstrate, and an organic EL substrate.

One suitable mode of use of the cleaning agent composition of thepresent invention in semiconductor processing is use thereof in a methodfor producing a processed substrate (e.g., a thinned substrate) employedin semiconductor packaging techniques such as TSV.

More specifically, the cleaning agent composition of the presentinvention is used as a cleaning agent composition in a processedsubstrate production method including a first step of producing alaminate including a semiconductor substrate, a support substrate, andan adhesive layer formed from an adhesive composition; a second step ofprocessing the semiconductor substrate of the produced laminate; a thirdstep of separating the semiconductor substrate after processing; and afourth step of removing an adhesive residue remaining on the separatedsemiconductor substrate with the cleaning agent composition.

Typically, the adhesive composition used in the first step for formingan adhesive layer may be at least one species selected from the groupconsisting of a silicone adhesive (i.e., a polysiloxane adhesive), anacrylic resin adhesive, an epoxy resin adhesive, a polyamide adhesive, apolystyrene adhesive, a polyimide adhesive, and a phenolic resinadhesive. Particularly for removing a polysiloxane adhesive, thecleaning agent composition of the present invention is effectively used.Among polysiloxane adhesives, the cleaning agent composition of thepresent invention is effective for removing an adhesive residueoriginating from a polysiloxane adhesive containing a component (A)which is cured through hydrosilylation.

Thus, next will be described a method for producing a processedsubstrate by use of a polysiloxane adhesive (adhesive composition)containing a component (A) which is cured through hydrosilylation, andthe cleaning agent composition of the present invention. However,needless to say, the present invention is not limited to this productionmethod.

Firstly, there will be described the first step of producing a laminateincluding a semiconductor substrate, a support substrate, and anadhesive layer formed from an adhesive composition.

The component (A) which is contained in the adhesive composition andwhich is cured through hydrosilylation contains, for example, apolysiloxane (A1) having one or more units selected from the groupconsisting of a siloxane unit represented by SiO₂ (unit Q), a siloxaneunit represented by R¹R²R³SiO_(2/2) (unit M), a siloxane unitrepresented by R⁴R⁵SiO_(2/2) (unit D), and a siloxane unit representedby R⁶SiO_(3/2) (unit T), and a platinum group metal catalyst (A2);wherein the polysiloxane (A1) contains a polyorganosiloxane (a1) havingone or more units selected from the group consisting of a siloxane unitrepresented by SiO₂ (unit Q′), a siloxane unit represented byR^(1′)R^(2′)R^(3′)SiO_(1/2) (unit M′), a siloxane unit represented byR^(4′)R^(5′)SiO_(2/2) (unit D′), and a siloxane unit represented byR^(6′)SiO_(3/2) (unit T′), and at least one unit selected from the groupconsisting of unit M′, unit D′, and unit I′, and a polyorganosiloxane(a2) having one or more units selected from the group consisting of asiloxane unit represented by SiO₂ (unit Q″), a siloxane unit representedby R^(1″)R^(2″)R^(3″)SiO_(1/2) (unit M″), a siloxane unit represented byR^(4″)R^(5″)SiO_(2/2) (unit D″), and a siloxane unit represented byR^(6″)SiO_(3/2) (unit I″), and at least one unit selected from the groupconsisting of unit M″, unit D″, and unit T″.

Each of R¹ to R⁶ is a group or an atom bonded to a silicon atom andrepresents an alkyl group, an alkenyl group, or a hydrogen atom.

Each of R^(1′) to R^(6′) is a group bonded to a silicon atom andrepresents an alkyl group or an alkenyl group, and at least one ofR^(1′) to R^(6′) is an alkenyl group.

Each of R^(1″) to R^(6″) is a group or an atom bonded to a silicon atomand represents an alkyl group or a hydrogen atom, and at least one ofR^(1″) to R^(6″) is a hydrogen atom.

The alkyl group may be linear-chain, branched-chain, or cyclic. However,a linear-chain alkyl group and a branched-chain alkyl group arepreferred. No particular limitation is imposed on the number of carbonatoms thereof, and the number of carbon atoms is generally 1 to 40,preferably 30 or less, more preferably 20 or less, still more preferably10 or less.

Specific examples of the linear-chain or branched-chain alkyl groupinclude, but are not limited to, methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl,2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl,1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl,1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl,4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl,1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl,3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl,1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl,1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl.

Of these, methyl is preferred.

Specific examples of the cycloalkyl group include, but are not limitedto, cycloalkyl groups such as cyclopropyl, cyclobutyl,1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl,1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl,1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl,2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl,2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl,2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl,1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl,2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl,3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl,1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl,1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl,2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl,2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and2-ethyl-3-methyl-cyclopropyl; and bicycloalkyl groups such asbicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl,bicyclononyl, and bicyclodecyl.

The alkenyl group may be linear-chain or branched-chain. No particularlimitation is imposed on the number of carbon atoms thereof, and thenumber of carbon atoms is generally 2 to 40, preferably 30 or less, morepreferably 20 or less, still more preferably 10 or less.

Specific examples of the alkenyl group include, but are not limited to,ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl,2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl,1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl,2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl,1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl,2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl,2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl,1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl,2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl,4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl,1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylethenyl,2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl,2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl,3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl,3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl,4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-s-butylethenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,1-i-butylethenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-i-propyl-2-propenyl,3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl,1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-t-butylethenyl,1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl,1-ethyl-2-methyl-2-propenyl, 1-i-propyl-1-propenyl,1-i-propyl-2-propenyl, 1-methyl-2-cyclopentenyl,1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl,2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl,2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl,2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl,3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl,3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl,3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, and3-cyclohexenyl.

Of these, ethenyl and 2-propenyl are preferred.

As described above, the polysiloxane (A1) includes thepolyorganosiloxane (a1) and the polyorganosiloxane (a2). In curing, thealkenyl group present in the polyorganosiloxane (a1) and the hydrogenatom (Si—H group) present in the polyorganosiloxane (a2) form across-linking structure through hydrosilylation in the presence of theplatinum group metal catalyst (A2).

The polyorganosiloxane (a1) has one or more units selected from thegroup consisting of unit Q′, unit M′, unit D′, and unit T′, and at leastone unit selected from the group consisting of unit M′, unit D′, andunit T′. Two or more polyorganosiloxanes satisfying the above conditionsmay be used in combination as the polyorganosiloxane (a1).

Examples of preferred combinations of two or more units selected fromthe group consisting of unit Q′, unit M′, unit D′, and unit T′ include,but are not limited to, (unit Q′ and unit M′), (unit D′ and unit M′),(unit T′ and unit M′), and (unit Q′, unit T′, and unit M′).

In the case where the polyorganosiloxane (a1) includes two or morepolyorganosiloxanes, examples of preferred combinations include, but arenot limited to, (unit Q′ and unit M′)+(unit D′ and unit M′); (unit T′and unit M′)+(unit D′ and unit M′); and (unit Q′, unit T′, and unitM′)+(unit T′ and unit M′).

The polyorganosiloxane (a2) has one or more units selected from thegroup consisting of unit Q″, unit M″, unit D″, and unit T″, and at leastone unit selected from the group consisting of unit M″, unit D″, andunit T″. Two or more polyorganosiloxanes satisfying the above conditionsmay be used in combination as the polyorganosiloxane (a2).

Examples of preferred combinations of two or more units selected fromthe group consisting of unit Q″, unit M″, unit D″, and unit T″ include,but are not limited to, (unit M″ and unit D″), (unit Q″ and unit M″),and (unit Q″, unit T″, and unit M″).

The polyorganosiloxane (a1) is formed of siloxane units in which analkyl group and/or an alkenyl group is bonded to a silicon atom. Thealkenyl group content of the entire substituents R^(1′) to R^(6′) ispreferably 0.1 mol % to 50.0 mol %, more preferably 0.5 mol % to 30.0mol %, and the remaining R^(1′) to R^(6′) may be alkyl groups.

The polyorganosiloxane (a2) is formed of siloxane units in which analkyl group and/or a hydrogen atom is bonded to a silicon atom. Thehydrogen atom content of the entire substituents or atoms R¹″ to R⁶″ ispreferably 0.1 mol % to 50.0 mol %, more preferably 10.0 mol % to 40.0mol %, and the remaining R¹″ to R⁶″ may be alkyl groups.

The polysiloxane (A1) includes the polyorganosiloxane (a1) and thepolyorganosiloxane (a2). In one preferred embodiment of the presentinvention, the ratio by mole of alkenyl groups present in thepolyorganosiloxane (a1) to hydrogen atoms forming Si—H bonds present inthe polyorganosiloxane (a2) is 1.0:0.5 to 1.0:0.66.

The weight average molecular weight of each of the polyorganosiloxane(a1) and the polyorganosiloxane (a2) are generally 500 to 1,000,000,preferably 5,000 to 50,000.

Meanwhile, weight average molecular weight may be determined by meansof, for example, a GPC apparatus (EcoSEC, HLC-8320GPC, products of TosohCorporation) and GPC columns (Shodex(registered trademark), KF-803L,KF-802, and KF-801, products of Showa Denko K.K.) at a columntemperature of 40° C. and a flow rate of 1.0 mL/min by use oftetrahydrofuran as an eluent (extraction solvent) and polystyrene(product of Sigma-Aldrich) as a standard substance.

The polyorganosiloxane (a1) and the polyorganosiloxane (a2) contained inthe adhesive composition react with each other via hydrosilylation, tothereby form a cured film. Thus, the curing mechanism differs from themechanism of curing mediated by, for example, silanol groups. Therefore,neither of the siloxanes of the present invention is required to have asilanol group or a functional group forming a silanol group throughhydrolysis (e.g., an alkyloxy group).

The component (A) contains the platinum group metal catalyst (A2).

The platinum-based metallic catalyst is used to acceleratehydrosilylation between alkenyl groups of the polyorganosiloxane (a1)and Si—H groups of the polyorganosiloxane (a2).

Specific examples of the platinum-based metallic catalyst include, butare not limited to, platinum catalysts such as platinum black,platinum(II) chloride, chloroplatinic acid, a reaction product ofchloroplatinic acid and a monohydric alcohol, a chloroplatinicacid-olefin complex, and platinum bis(acetoacetate).

Examples of the platinum-olefin complex include, but are not limited to,a complex of platinum with divinyltetramethyldisiloxane.

The amount of platinum group metal catalyst (A2) is generally 1.0 to50.0 ppm, with respect to the total amount of polyorganosiloxane (a1)and polyorganosiloxane (a2).

The component (A) may contain a polymerization inhibitor (A3). Throughincorporation of the polymerization inhibitor into an adhesivecomposition, heat curing during bonding can be suitably controlled,whereby an adhesive composition which can provide an adhesive layerhaving an excellent bonding/debonding property can be produced at highreproducibility.

No particular limitation is imposed on the polymerization inhibitor, solong as it can suppress the progress of hydrosilylation. Specificexamples of the polymerization inhibitor include, but are not limitedto, alkynylalkyl alcohols such as 1-ethynyl-1-cyclohexanol and1,1-diphenyl-2-propyn-1-ol.

Generally, the amount of polymerization inhibitor with respect to thepolyorganosiloxane (a1) and the polyorganosiloxane (a2) is 1,000.0 ppmor more from the viewpoint of attaining the effect, and 10,000.0 ppm orless from the viewpoint of preventing excessive suppression ofhydrosilylation.

The adhesive composition may contain a component (B) containing at leastone species selected from the group consisting of a component containingan epoxy-group-containing polyorganosiloxane, a component containing amethyl-group-containing polyorganosiloxane, and a component containing aphenyl-group-containing polyorganosiloxane. Through incorporation ofsuch a component (B) into the adhesive composition, the formed adhesivelayer can be suitably peeled off at high reproducibility.

The epoxy-group-containing polyorganosiloxane includes, for example,such a siloxane containing a siloxane unit represented by, for example,R¹¹R¹²SiO_(2/2) (unit D¹⁰).

R¹¹ is a group bonded to a silicon atom and represents an alkyl group,and R¹² is a group bonded to a silicon atom and represents an epoxygroup or an organic group containing an epoxy group. Specific examplesof the alkyl group include those as exemplified above.

Also, the epoxy group in the organic group containing an epoxy group maybe an independent epoxy group which does not condense with another ringstructure, or may be an epoxy group forming a condensed ring withanother ring structure (e.g., a 1,2-epoxycyclohexyl group).

Specific examples of the organic group containing an epoxy groupinclude, but are not limited to, 3-glycidoxypropyl and2-(3,4-epoxycyclohexyl)ethyl.

In the present invention, examples of preferred epoxy-group-containingpolyorganosiloxanes include, but are not limited to,epoxy-group-containing polydimethylsiloxane.

The epoxy-group-containing polyorganosiloxane contains theaforementioned siloxane unit (unit D¹⁰), but may also contain theaforementioned unit Q, unit M and/or unit T, in addition to unit D¹⁰.

In one preferred embodiment, specific examples of theepoxy-group-containing polyorganosiloxane include polyorganosiloxaneformed only of unit D¹⁰, polyorganosiloxane formed of unit D¹⁰ and unitQ, polyorganosiloxane formed of unit D¹⁰ and unit M, polyorganosiloxaneformed of unit D¹⁰ and unit T, polyorganosiloxane formed of unit D¹⁰,unit Q, and unit M, polyorganosiloxane formed of unit D¹⁰, unit M, andunit T, and polyorganosiloxane formed of unit D¹⁰, unit Q, unit M, andunit T.

The epoxy-group-containing polyorganosiloxane is preferably anepoxy-group-containing polydimethylsiloxane having an epoxy value of 0.1to 5. The weight average molecular weight thereof is generally 1,500 to500,000, but preferably 100,000 or lower, for the purpose of suppressionof precipitation in the adhesive composition.

Specific examples of the epoxy-group-containing polyorganosiloxaneinclude, but are not limited to, CMS-227 (product of Gelest Inc., weightaverage molecular weight: 27,000) represented by formula (A-1), ECMS-327(product of Gelest Inc., weight average molecular weight: 28,800)represented by formula (A-2), KF-101 (product of Shin-Etsu Chemical Co.,Ltd., weight average molecular weight: 31,800) represented by formula(A-3), KF-1001 (product of Shin-Etsu Chemical Co., Ltd., weight averagemolecular weight: 55,600) represented by formula (A-4), KF-1005 (productof Shin-Etsu Chemical Co., Ltd., weight average molecular weight:11,500) represented by formula (A-5), X-22-343 (product of Shin-EtsuChemical Co., Ltd., weight average molecular weight: 2,400) representedby formula (A-6), BY16-839 (product of Dow Corning, weight averagemolecular weight: 51,700) represented by formula (A-7), and ECMS-327(product of Gelest Inc., weight average molecular weight: 28,800)represented by formula (A-8).

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units. R representsa C1 to C10 alkylene group.)

(Each of m and n represents the number of repeating units. R representsa C1 to 010 alkylene group.)

(Each of m, n and o represents the number of repeating units. Rrepresents a C1 to C10 alkylene group.)

(Each of m and n represents the number of repeating units. R representsa C1 to C10 alkylene group.)

(Each of m and n represents the number of repeating units. R representsa C1 to 010 alkylene group.)

(Each of m and n represents the number of repeating units.)

The methyl-group-containing polyorganosiloxane includes, for example, asiloxane containing a siloxane unit represented by R²¹⁰R²²⁰SiO_(2/2)(unit D²⁰⁰), preferably a siloxane containing a siloxane unitrepresented by R²¹R²¹SiO_(2/2) (unit D²⁰).

Each of R²¹⁰ and R²²⁰ is a group bonded to a silicon atom and representsan alkyl group. At least one of R²¹⁰ and R²²⁰ is a methyl group.Specific examples of the alkyl group include those as exemplified above.

R²¹ is a group bonded to a silicon atom and represents an alkyl group.Specific examples of the alkyl group include those as exemplified above.Rn is preferably a methyl group.

Examples of preferred methyl-group-containing polyorganosiloxanesinclude, but are not limited to, polydimethylsiloxane.

The methyl-group-containing polyorganosiloxane contains theaforementioned siloxane unit (unit D²⁰⁰ or unit D²⁰), but may alsocontain the aforementioned unit Q, unit M and/or unit T, in addition tounit D²⁰⁰ or unit D²⁰.

In one embodiment, specific examples of the methyl-group-containingpolyorganosiloxane include polyorganosiloxane formed only of unit D²⁰⁰,polyorganosiloxane formed of unit D²⁰⁰ and unit Q, polyorganosiloxaneformed of unit D²⁰⁰ and unit M, polyorganosiloxane formed of unit D²⁰⁰and unit T, polyorganosiloxane formed of unit D²⁰⁰, unit Q, and unit M,polyorganosiloxane formed of unit D²⁰⁰, unit M, and unit T, andpolyorganosiloxane formed of unit D²⁰⁰, unit Q, unit M, and unit T.

In one preferred embodiment, specific examples of themethyl-group-containing polyorganosiloxane include polyorganosiloxaneformed only of unit D²⁰, polyorganosiloxane formed of unit D²⁰ and unitQ, polyorganosiloxane formed of unit D²⁰ and unit M, polyorganosiloxaneformed of unit D²⁰ and unit T, polyorganosiloxane formed of unit D²⁰,unit Q, and unit M, polyorganosiloxane formed of unit D²⁰, unit M, andunit T, and polyorganosiloxane formed of unit D²⁰, unit Q, unit M, andunit T.

The viscosity of the methyl-group-containing polyorganosiloxane isgenerally 1,000 to 2,000,000 mm²/s, preferably 10,000 to 1,000,000mm²/s. The methyl-group-containing polyorganosiloxane is typicallydimethylsilicone oil formed of polydimethylsiloxane. The value of theviscosity is a kinematic viscosity (cSt (=mm²/s)). The kinematicviscosity may be measured by means of a kinematic viscometer.Alternatively, the kinematic viscosity may also be calculated bydividing viscosity (mPa·s) by density (g/cm³). In other words, thekinematic viscosity may be determined from a viscosity as measured at25° C. by means of an E-type rotational viscometer and a density. Thecalculation formula is kinematic viscosity (mm²/s)=viscosity(mPa·s)/density (g/cm³).

Specific examples of the methyl-group-containing polyorganosiloxaneinclude, but are not limited to, WACKER(registered trademark) SILICONEFLUID AK series (products of WACKER) and dimethylsilicone oils (KF-96L,KF-96A, KF-96, KF-96H, KF-69, KF-965, and KF-968) and cyclicdimethylsilicone oil (KF-995) (products of Shin-Etsu Chemical Co.,Ltd.).

Examples of the phenyl-group-containing polyorganosiloxane include asiloxane containing a siloxane unit represented by R³¹R³²SiO_(2/2) (unitD³⁰).

R³¹ is a group bonded to a silicon atom and represents a phenyl group oran alkyl group, and R³² is a group bonded to a silicon atom andrepresents a phenyl group. Specific examples of the alkyl group includethose as exemplified above. R³¹ is preferably a methyl group.

The phenyl-group-containing polyorganosiloxane contains theaforementioned siloxane unit (unit D³⁰), but may also contain theaforementioned unit Q, unit M and/or unit T, in addition to unit D³⁰.

In one preferred embodiment, specific examples of thephenyl-group-containing polyorganosiloxane include polyorganosiloxaneformed only of unit D³⁰, polyorganosiloxane formed of unit D³⁰ and unitQ, polyorganosiloxane formed of unit D³⁰ and unit M, polyorganosiloxaneformed of unit D³⁰ and unit T, polyorganosiloxane formed of unit D³⁰,unit Q, and unit M, polyorganosiloxane formed of unit D³⁰, unit M, andunit T, and polyorganosiloxane formed of unit D³⁰, unit Q, unit M, andunit T.

The weight average molecular weight of the phenyl-group-containingpolyorganosiloxane is generally 1,500 to 500,000, but preferably 100,000or lower, for the purpose of suppression of precipitation in theadhesive composition and for other reasons.

Specific examples of the phenyl-group-containing polyorganosiloxaneinclude, but are not limited to, PMM-1043 (product of Gelest Inc.,weight average molecular weight: 67,000, viscosity: 30,000 mm²/s)represented by formula (C-1), PMM-1025 (product of Gelest Inc., weightaverage molecular weight: 25,200, viscosity: 500 mm²/s) represented byformula (C-2), KF50-3000CS (product of Shin-Etsu Chemical Co., Ltd.,weight average molecular weight: 39,400, viscosity: 3,000 mm²/s)represented by formula (C-3), TSF431 (product of MOMENTIVE, weightaverage molecular weight: 1,800, viscosity: 100 mm²/s) represented byformula (C-4), TSF433 (product of MOMENTIVE, weight average molecularweight: 3,000, viscosity: 450 mm²/s) represented by formula (C-5),PDM-0421 (product of Gelest Inc., weight average molecular weight:6,200, viscosity: 100 mm²/s) represented by formula (C-6), and PDM-0821(product of Gelest Inc., weight average molecular weight: 8,600,viscosity: 125 mm²/s) represented by formula (C-7).

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

(Each of m and n represents the number of repeating units.)

The polysiloxane adhesive composition contains the components (A) and(B) at any compositional ratio. In consideration of the balance betweenbonding performance and debonding performance, the compositional ratio(mass %) of component (A) to component (B) is preferably 99.995:0.005 to30:70, more preferably 99.9:0.1 to 75:25.

For the purpose of adjusting the viscosity or for other reasons, theadhesive composition may contain a solvent. Specific examples of thesolvent include, but are not limited to, an aliphatic hydrocarbon, anaromatic hydrocarbon, and a ketone.

More specific examples of the solvent include, but are not limited to,hexane, heptane, octane, nonane, decane, undecane, dodecane,isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene,MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone,2-octanone, 2-nonanone, and 5-nonanone. These solvents may be usedsingly or in combination of two or more species.

In the case where the adhesive composition contains a solvent, thesolvent content is appropriately adjusted in consideration of a targetviscosity of the adhesive composition, the application method to beemployed, the thickness of the formed thin film, etc. The solventcontent of the entire composition is about 10 to about 90 mass %.

The adhesive composition generally has a viscosity (25° C.) of 1,000 to20,000 mPa·s. The viscosity may be controlled by modifying the type andformulation of the solvent used, the film-forming componentconcentration, etc., in consideration of various factors such as thecoating method employed and the target film thickness.

The adhesive composition used in the present invention may be producedby mixing film-forming components with solvent. However, in the casewhere no solvent is used, the adhesive composition used in the presentinvention may be produced by mixing film-forming components.

No particular limitation is imposed on the sequential order of mixing,so long as the adhesive composition of the present invention can beeasily produced at high reproducibility. One possible example of theproduction method includes dissolving all film-forming components in asolvent. Another possible example of the production method includesdissolving a part of film-forming components in a solvent, dissolvingthe other film-forming components in another solvent, and mixing the twothus-obtained solutions. In this case, if required, a part of thesolvent or a film-forming component having high dissolvability may beadded in a final stage.

So long as the relevant components are not decomposed or denatured inpreparation of the adhesive composition, the mixture may beappropriately heated. Also, in order to remove foreign substancespresent in the adhesive composition, the composition may be filteredthrough a sub-micrometer filter or the like in the course of productionof the composition or after mixing all the components.

The first step of the processed substrate production method specificallyincludes a primary step and a subsequent step. In the primary step, theadhesive composition is applied onto a surface of the semiconductorsubstrate or the support substrate, to thereby form an adhesive coatinglayer. In the subsequent step, the semiconductor substrate is adhered tothe support substrate by the mediation of the adhesive coating layer,and a load is applied to the semiconductor substrate and the supportsubstrate in a thickness direction, to thereby closely adhere thesemiconductor substrate, the adhesive coating layer, and the supportsubstrate, while at least one of a heat treatment and a reduced pressuretreatment is performed. Then, a post-heat treatment is performed.Through the post-heat treatment in the subsequent step, the adhesivecoating layer is suitably cured in a final stage to form an adhesivelayer. Thus, a laminate is provided.

In one embodiment, the semiconductor substrate is a wafer, and thesupport substrate is a support. The adhesive composition may be appliedto either of the semiconductor or support substrate, or both of thesemiconductor and support substrates.

No particular limitation is imposed on the wafer. Examples of the waferinclude, but are not limited to, a silicon wafer or a glass wafer havinga diameter of about 300 mm and a thickness of about 770 μm.

No particular limitation is imposed on the support (carrier). Examplesof the support include, but are not limited to, a silicon wafer having adiameter of about 300 mm and a thickness of about 700 μm.

The thickness of the aforementioned adhesive coating layer is generally5 to 500 μm. However, the thickness is preferably 10 μm or greater, morepreferably 20 μm or greater, still more preferably 30 μm or greater,from the viewpoint of maintaining the film strength, and it ispreferably 200 μm or less, more preferably 150 μm or less, still morepreferably 120 μm or less, yet more preferably 70 μm or less, from theviewpoint of avoiding variation in uniformity of the film thickness.

No particular limitation is imposed on the application method, and spincoating is generally employed. In an alternative method, a coating filmis formed through spin coating or a similar technique, and thesheet-form coating film is attached. The concepts of the applicationmethod and the coating film of the invention also encompass thealternative method and coating film.

The heating temperature is generally 80° C. or higher, preferably 150°C. or lower, from the viewpoint of prevention of excessive curing. Thetime of heating is generally 30 seconds or longer, preferably 1 minuteor longer, for securing temporary bonding performance. Also, the heatingtime is generally 10 minutes or shorter, preferably 5 minutes orshorter, from the viewpoint of suppressing deterioration of the adhesivelayer and other members.

In the reduced pressure treatment, the two substrates and the adhesivecoating layer disposed therebetween are placed in an atmosphere at 10 Pato 10,000 Pa. The time of the reduced pressure treatment is generally 1to 30 minutes.

In one preferred embodiment of the present invention, the two substratesand the adhesive coating layer disposed therebetween are bonded togetherpreferably through a heat treatment, more preferably through a heattreatment in combination with a reduced pressure treatment.

No particular limitation is imposed on the load which is applied to thesemiconductor substrate and the support substrate in a thicknessdirection, so long as the semiconductor substrate, the supportsubstrate, and the layer disposed therebetween are not damaged, andthese elements are closely adhered. The load is generally 10 to 1,000 N.

The temperature of post-heating is preferably 120° C. or higher from theviewpoint of attaining sufficient curing rate, and preferably 260° C. orlower from the viewpoint of preventing deterioration of the substratesand the adhesives. The heating time is generally 1 minute or longer fromthe viewpoint of joining of a wafer through curing, preferably 5 minutesor longer from the viewpoint of, for example, stability in physicalproperties of the adhesives. Also, the heating time is generally 180minutes or shorter, preferably 120 minutes or shorter, from theviewpoint of avoiding, for example, an adverse effect on the adhesivelayers due to excessive heating. Heating may be performed by means of ahot plate, an oven, or the like. Notably, a purpose of performingpost-heating is to, for example, more suitably cure the component (A).

There will next be described the second step for processing thesemiconductor substrate of the laminate produced through theaforementioned method.

One example of the processing applied to the laminate used in thepresent invention is processing of a surface opposite thecircuit-furnished surface of the semiconductor substrate. Typically, theprocessing is thinning a wafer by polishing (grinding) the backsidethereof. Thereafter, the thinned wafer is provided with silicon vias(TSVs) and the like and then removed from the support. A plurality ofsuch wafers are stacked to form a wafer laminate, to thereby complete3-dimensional mounting. Before or after the above process, a backsideelectrode and the like are formed on the wafer. When thinning of a waferand the TSV process are performed, a thermal load of 250 to 350° C. isapplied to the laminate bonded to the support. The adhesive layerincluded in the laminate used in the present invention has heatresistance to the load.

In one specific embodiment, when the backside surface (a surfaceopposite the circuit-furnished surface) of a wafer having a diameter ofabout 300 mm and a thickness of about 770 μm is polished (ground), thethickness of the wafer can be reduced to about 80 μm to about 4 μm.

Next will be described the third step of debonding the semiconductorsubstrate after processing.

Examples of the laminate debonding method employed in the presentinvention include, but are not limited to, debonding with solvent,debonding with laser light, mechanical debonding by means of a machinemember having a sharp part, and peeling between a support and a wafer.Generally, debonding is performed after processing (e.g., thinning).

In the third step, the adhesive is not always removed while the adhesiveis firmly attached to the support substrate, and in some cases, a partof the adhesive may remain on the processed substrate. Thus, in thefourth step, the surface of the substrate on which the adhesive residueis deposited is cleaned by use of the aforementioned cleaning agentcomposition of the present invention. As a result, the adhesiveremaining on the substrate can be satisfactorily removed.

Finally, the fourth step will be described. In the fourth step, theadhesive residue remaining on the debonded semiconductor substrate isremoved by use of the cleaning agent composition.

The fourth step corresponds to removing the adhesive residue remainingon the surface of the debonded substrate by use of the cleaning agentcomposition of the present invention. In one specific procedure, athinned substrate on which an adhesive remains is immersed in thecleaning agent composition of the present invention and, if required,subjected to ultrasonic cleaning or the like, to thereby remove theadhesive residue.

When ultrasonic cleaning is employed, the cleaning conditions areappropriately determined in consideration of the surface state of thesubstrate. Generally, through ultrasonic cleaning at 20 kHz to 5 MHz for10 seconds to 30 minutes, the adhesive residue remaining on thesubstrate can be satisfactorily removed.

The method of the present invention for producing a processed substrate(e.g., a thinned substrate) includes the aforementioned first to fourthsteps, but may further include another step. For example, in the fourthstep, before cleaning with the cleaning agent composition of the presentinvention, if required, the substrate may be immersed in varioussolvents, or subjected to tape peeling, to thereby remove the adhesiveresidue.

Notably, the aforementioned elements in terms of configuration andmethod employed in the first to fourth steps may be modified in variousways, so long as the modifications do not deviate from the scope of thepresent invention.

EXAMPLES

The present invention will next be described in detail by way ofExamples and Comparative Examples, which should not be construed aslimiting the invention thereto. The apparatuses employed in the presentinvention are as follows.

(1) Agitator: Planetary centrifugal mixer ARE-500 (product of ThinkyCorporation)

(2) Viscometer: Rotary viscometer TVE-22H (product of Toki Sangyo Co.,Ltd)

(3) Agitator: Mix Roter Variable 1-1186-12 (product of As OneCorporation)

(4) Agitator H: Heating Rocking Mixer HRM-1 (product of As OneCorporation)

(5) Contact-type film thickness meter: Wafer thickness meter WT-425(product of Tokyo Seimitsu Co., Ltd.)

[1] Preparation of Adhesive Compositions

Preparation Example 1

To a 600-mL agitation container dedicated for a planetary centrifugalmixer, there were added a base polymer formed of linear-chainpolydimethylsiloxane having vinyl groups (viscosity: 200 mPa·s) and anMQ resin having vinyl groups (product of WACKER Chemie AG) (a1) (150 g),linear-chain polydimethylsiloxane having Si—H groups (viscosity: 100mPa·s) (product of WACKER Chemie AG) (a2) (15.81 g), and1-ethynyl-1-cyclohexanol (product of WACKER Chemie AG) (A3) (0.17 g),and the resultant mixture was agitated by means of a planetarycentrifugal mixer for 5 minutes.

Separately, a platinum catalyst (product of WACKER Chemie AG) (A2) (0.33g) and linear-chain polydimethylsiloxane having vinyl groups (viscosity:1,000 mPa·s) (product of WACKER Chemie AG) (a1) (9.98 g) were added to a50-mL screw tube, and the contents were agitated for 5 minutes by meansof a planetary centrifugal mixer. A portion (0.52 g) of thethus-agitated mixture was added to the above mixture, and the resultantmixture was agitated for 5 minutes by means of a planetary centrifugalmixer. Finally, the product mixture was filtered through a nylon filter(300 mesh), to thereby prepare an adhesive composition having aviscosity of 9,900 mPa·s as determined by means of a rotary viscometer.

Preparation Example 2

To a 600-mL agitation container dedicated for a planetary centrifugalmixer, a base polymer formed of an MQ resin having vinyl groups (productof WACKER Chemie AG) (a1) (95 g), p-menthane (product of Nippon TerpeneChemicals, Inc.) (93.4 g) serving as a solvent, and1,1-diphenyl-2-propyn-1-ol (product of Tokyo Chemical Industry Co.,Ltd.) (A3) (0.41 g) were added, and the resultant mixture was agitatedfor 5 minutes by means of a planetary centrifugal mixer.

To the thus-prepared mixture, there were added linear-chainpolydimethylsiloxane having Si—H groups (viscosity: 100 mPa·s) (productof WACKER Chemie AG) (a2), linear-chain polydimethylsiloxane havingvinyl groups (viscosity: 200 mPa·s) (product of WACKER Chemie AG) (a1)(29.5 g), polyorganosiloxane (polydimethylsiloxane, viscosity: 1,000,000mm²/s) (AK1000000, product of WACKER Chemie AG) (B), and1-ethynyl-1-cyclohexanol (product of WACKER Chemie AG) (A3) (0.41 g),and the resultant mixture was further agitated for 5 minutes by means ofa planetary centrifugal mixer.

Separately, a platinum catalyst (product of WACKER Chemie AG) (A2) (0.20g) and linear-chain polydimethylsiloxane having vinyl groups (viscosity:1,000 mPa·s) (product of WACKER Chemie AG) (a1) (17.7 g) were added to a50-mL screw tube, and the contents were agitated for 5 minutes by meansof a planetary centrifugal mixer. A portion (14.9 g) of thethus-agitated mixture was added to the above mixture, and the resultantmixture was further agitated for 5 minutes by means of the planetarycentrifugal mixer. Finally, the product mixture was filtered through anylon filter (300 mesh), to thereby prepare an adhesive compositionhaving a viscosity of 4,600 mPa·s as determined by means of a rotaryviscometer.

[2] Preparation of Cleaning Agent Compositions

Example 1

N,N-Dimethylpropionamide (14.25 g) and 1,2-diethoxyethane (14.25 g) wereadded to tetrabutylammonium fluoride trihydrate (product of KantoChemical Co., Inc.) (1.50 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 2

N,N-Dimethylpropionamide (11.18 g) and tetrahydrofuran (11.18 g) wereadded to tetrabutylammonium fluoride trihydrate (product of KantoChemical Co., Inc.) (1.18 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 3

N,N-Dimethylpropionamide (20.08 g) and tetrahydropyran (20.08 g) wereadded to tetrabutylammonium fluoride trihydrate (product of KantoChemical Co., Inc.) (2.11 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 4

N,N-Dimethylpropionamide (17.81 g) and cyclopentyl methyl ether (17.81g) were added to tetrabutylammonium fluoride trihydrate (product ofKanto Chemical Co., Inc.) (1.88 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 5

N,N-Dimethylpropionamide (10.25 g) and mesitylene (10.25 g) were addedto tetrabutylammonium fluoride trihydrate (product of Kanto ChemicalCo., Inc.) (1.08 g), and the thus-obtained mixture was agitated, tothereby prepare a cleaning agent composition.

Example 6

N,N-Dimethylisobutylamide (12.52 g) and 1,2-diethoxyethane (12.52 g)were added to tetrabutylammonium fluoride trihydrate (product of KantoChemical Co., Inc.) (1.32 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 7

N,N-Dimethylisobutylamide (12.52 g) and tetrahydrofuran (12.52 g) wereadded to tetrabutylammonium fluoride trihydrate (product of KantoChemical Co., Inc.) (1.32 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 8

N,N-Dimethylisobutylamide (12.52 g) and tetrahydropyran (12.52 g) wereadded to tetrabutylammonium fluoride trihydrate (product of KantoChemical Co., Inc.) (1.32 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 9

N,N-Dimethylisobutylamide (12.52 g) and cyclopentyl methyl ether (12.52g) were added to tetrabutylammonium fluoride trihydrate (product ofKanto Chemical Co., Inc.) (1.32 g), and the thus-obtained mixture wasagitated, to thereby prepare a cleaning agent composition.

Example 10

N,N-Dimethylisobutylamide (12.52 g) and mesitylene (12.52 g) were addedto tetrabutylammonium fluoride trihydrate (product of Kanto ChemicalCo., Inc.) (1.32 g), and the thus-obtained mixture was agitated, tothereby prepare a cleaning agent composition.

Comparative Example 1

N,N-Dimethylacetamide (9.50 g) was added to tetrabutylammonium fluoridetrihydrate (product of Kanto Chemical Co., Inc.) (0.50 g), and thethus-obtained mixture was agitated, to thereby prepare a cleaning agentcomposition.

Comparative Example 2

1,3-Dimethyl-2-imidazolidinone (95 g) was added to tetrabutylammoniumfluoride trihydrate (product of Kanto Chemical Co., Inc.) (5 g), and thethus-obtained mixture was agitated, to thereby prepare a cleaning agentcomposition.

Comparative Example 3

N-Methyl-2-pyrrolidone (dehydrated) (95 g) was added totetrabutylammonium fluoride trihydrate (product of Kanto Chemical Co.,Inc.) (5 g), and the thus-obtained mixture was agitated, to therebyprepare a cleaning agent composition.

Comparative Example 4

N,N-Dimethylpropionamide (product of Tokyo Chemical Industry Co., Ltd.)(47.5 g) and tetrahydrofuran (product of Kanto Chemical Co., Inc.) (47.5g) were added to tetrabutylammonium fluoride trihydrate (product ofKanto Chemical Co., Inc.) (5 g), and the thus-obtained mixture wasagitated. Subsequently, pure water (5 g) was further added thereto, andthe resultant mixture was further agitated, to thereby prepare acleaning agent composition.

Comparative Example 5

A commercial silicone cleaner “KSR-1” (product of Kanto Chemical Co.,Inc.) was used as a cleaning liquid composition.

[3] Evaluation of Performance of Cleaning Agent Compositions

Generally, the excellent cleaning agent composition is required toexhibit such a high cleaning speed that it can dissolve an adhesiveresidue immediately after contact therewith, and excellent persistencyin cleaning speed. Thus, the following tests were performed. When atested cleaning agent composition exhibits both higher cleaning speedand more excellent persistency in cleaning performance, more effectivecleaning can be expected.

[3-1] Determination of Water Content

The water content of each cleaning agent composition was determined bymeans of a Karl Fischer moisture meter CA-200 (product of MitsubishiChemical Analytech).

[3-2] Determination of Etching Rate

Each of the prepared cleaning agent compositions was evaluated in termsof cleaning speed by measuring the etching rate. Specifically, theadhesive composition obtained in Preparation Example 1 was applied ontoa 12-inch silicon wafer by means of a spin coater so as to adjust thecoating thickness to 100 μm, and cured at 150° C. for 15 minutes, then190° C. for 10 minutes. The thus-coated wafer was cut into square chips(4 cm×4 cm), and the layer (film) thickness of one of the chips wasmeasured by means of a contact-type film thickness meter. Thereafter,the chip was placed in a 9-cm Petri dish made of stainless steel, andthe cleaning agent composition (7 mL) was added, followed by closing thedish. The closed Petri dish was placed on Agitator H, and the chip wascleaned through agitation at 23° C. for 5 minutes. After cleaning, thechip was removed and washed with isopropanol and pure water, and thendry-baked at 150° C. for 1 minute. The layer (film) thickness of thechip was measured again by means of the contact-type film thicknessmeter. Through dividing the decrease in layer (film) thickness aftercleaning by the cleaning time, etching rate [μm/min] was calculated. Theetching rate was employed as an index for cleaning performance. Table 1shows the results.

[3-3] Evaluation of Dissolution Property

For determining the persistency in cleaning performance of each of theprepared cleaning agent compositions, the following adhesive dissolutiontest was conducted. Specifically, the adhesive composition obtained inPreparation Example 2 was applied onto a 12-inch silicon wafer by meansof a spin coater and cured at 120° C. for 1.5 minutes and 200° C. for 10minutes. Subsequently, the cured adhesive composition was scraped off byuse of a cutter blade from the 12-inch wafer. A portion (1 g) of thecured adhesive composition was transferred to and weighed in a 9-mLscrew tube, and then the cleaning agent composition (2 g) was added tothe tube. The dissolution state of the cured product was observed at 23°C. When the cured product was completely dissolved within 1 to 2 hours,the state was rated as “Excellent.” When the cured product wascompletely dissolved within 2 to 12 hours, the state was rated as “Verygood.” When the cured product was substantially dissolved within 12 to24 hours, the state was rated as “Good.” When the cured product wassubstantially not dissolved over a long period of time, the state wasrated as “Bad.” Table 1 shows the results.

TABLE 1 Water content Etching rate Dissolution (%) [μm/min] test Ex. 10.67 10.8 Excellent Ex. 2 0.65 14.72 Excellent Ex. 3 0.67 10.62Excellent Ex. 4 0.63 11.51 Excellent Ex. 5 0.63 8.72 Excellent Ex. 60.63 10.28 Excellent Ex. 7 0.78 13.85 Excellent Ex. 8 0.73 9.93Excellent Ex. 9 0.71 10.26 Excellent Ex. 10 0.72 8.32 Very good Comp.Ex. 1 — 8 Bad Comp. Ex. 2 — 4 Bad Comp. Ex. 3 — 5.1 Bad Comp. Ex. 4 5.360.69 — Comp. Ex. 5 — 2.3 Bad

As shown in Table 1, the cleaning agent compositions, each containing aquaternary ammonium salt (i.e., tetrabutylammonium fluoride), an amidederivative represented by formula (Z) (i.e., N,N-dimethylpropionamide),and a non-amide solvent, fell within the scope of the present inventionand were found to exhibit excellent cleaning speed and favorablepersistency in cleaning performance, as compared with those of cleaningagent compositions each containing a solvent formed only of an amidederivative not represented by formula (Z) and a cleaning agentcomposition containing intentionally added water.

The invention claimed is:
 1. A cleaning agent composition for use inremoving an adhesive residue, the composition comprising a quaternaryammonium salt and a composition solvent including a first organicsolvent and a second organic solvent; the first organic solvent is anamide derivative represented by formula (Z):

wherein R⁰ represents an ethyl group, a propyl group, or an isopropylgroup; and each of R^(A) and R^(B) represents a C1 to C4 alkyl group;the second organic solvent is a non-amide organic solvent other than theamide derivative; the quaternary ammonium salt includes afluorine-containing quaternary ammonium salt; and the composition has awater content less than 4.0 mass %.
 2. The cleaning agent compositionaccording to claim 1, wherein the amide derivative includes at least onespecies selected from the group consisting of N,N-dimethylpropionamide,N,N-diethylpropionamide, N-ethyl-N-methylpropionamide,N,N-dimethylbutyramide, N,N-diethylbutyramide,N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide,N,N-diethylisobutyramide, and N-ethyl-N-methylisobutyramide.
 3. Thecleaning agent composition according to claim 2, wherein the amidederivative includes at least one species selected from the groupconsisting of N,N-dimethylpropionamide, N,N-diethylpropionamide,N,N-dimethylbutyramide, N,N-diethylbutyramide,N,N-dimethylisobutyramide, and N,N-diethylisobutyramide.
 4. The cleaningagent composition according to claim 3, wherein the amide derivativeincludes at least one species selected from the group consisting ofN,N-dimethylpropionamide and N,N-dimethylisobutyramide.
 5. The cleaningagent composition according to claim 1, wherein the fluorine-containingquaternary ammonium salt includes a tetra(hydrocarbyl)ammonium fluoride.6. The cleaning agent composition according to claim 5, wherein thetetra(hydrocarbyl)ammonium fluoride includes at least one speciesselected from the group consisting of tetramethylammonium fluoride,tetraethylammonium fluoride, tetrapropylammonium fluoride, andtetrabutylammonium fluoride.
 7. The cleaning agent composition accordingto claim 1, wherein the second organic solvent includes at least onespecies selected from the group consisting of an alkylene glycol dialkylether, an aromatic hydrocarbon compound, and a ring-structure-havingether compound.
 8. The cleaning agent composition according to claim 1,wherein the composition solvent is formed only of an organic solvent. 9.The cleaning agent composition according to claim 1, wherein thecomposition solvent has an amide derivative content of 30 to 90 mass %.10. The cleaning agent composition according to claim 1, which has awater content less than 3.0 mass %.
 11. The cleaning agent compositionaccording to claim 10, which has a water content less than 2.0 mass %.12. The cleaning agent composition according to claim 11, which has awater content less than 1.0 mass %.
 13. A cleaning method, comprisingremoving an adhesive residue remaining on a substrate by use of thecleaning agent composition as recited in claim
 1. 14. A method forproducing a processed semiconductor substrate, the method comprising:producing a laminate including a semiconductor substrate, a supportsubstrate, and an adhesive layer formed from an adhesive composition;processing the semiconductor substrate of the produced laminate;separating the semiconductor substrate after processing; and removing anadhesive residue remaining on the separated substrate with a cleaningagent composition, wherein the cleaning agent composition as recited inclaim 1 is used as the cleaning agent composition.